Selective etching processes of SiO2 , Ti and In2 O3 thin films for FeRAM device applications

ABSTRACT

A method of selectively etching a three-layer structure consisting of SiO 2 , In 2 O 3 , and titanium, includes etching the SiO 2 , stopping at the titanium layer, using C 3 F 8  in a range of between about 10 sccm to 30 sccm; argon in a range of between about 20 sccm to 40 sccm, using an RF source in a range of between about 1000 watts to 3000 watts and an RF bias in a range of between about 400 watts to 800 watts at a pressure in a range of between about 2 mtorr to 6 mtorr; and etching the titanium, stopping at the In 2 O 3  layer, using BCl in a range of between about 10 sccm to 50 sccm; chlorine in a range of between about 40 sccm to 80 sccm, a T cp  in a range of between about 200 watts to 500 watts at an RF bias in a range of between about 100 watts to 200 watts at a pressure in a range of between about 4 mtorr to 8 mtorr.

FIELD OF THE INVENTION

The present invention relates to ferroelectric memory device structures and specifically to an integrated process for fabricating ferroelectric non-volatile memory devices.

BACKGROUND OF THE INVENTION

A number of Metal/FE/In₂O₃/Si memory cells for one-transistor ferroelectric memory devices have been proposed, however, such a device requires formation of an oxide trench structure in the ferroelectric material, and selective deposition of In₂O₃ in the trench. This in turn requires an etching processes for SiO₂ which is stopped at a In₂O₃ layer. Such a process is not known at this time. Conductive Metal Oxide Gate Ferroelectric Memory Transistor, Ser. No. 10/659,547, filed Sep. 9, 2003 of Hsu et al., provides some background to this problem.

SUMMARY OF THE INVENTION

A method of selectively etching a three-layer structure consisting of SiO₂, In₂O₃, and titanium, includes etching the SiO₂, stopping at the titanium layer, using C₃F₈ in a range of between about 10 sccm to 30 sccm; argon in a range of between about 20 sccm to 40 sccm, using an RF source in a range of between about 1000 watts to 3000 watts and an RF bias in a range of between about 400 watts to 800 watts at a pressure in a range of between about 2 mtorr to 6 mtorr; and etching the titanium, stopping at the In₂O₃ layer, using BCl in a range of between about 10 sccm to 50 sccm; chlorine in a range of between about 40 sccm to 80 sccm, a T_(cp) in a rang watts to 200 watts at a pressure in a range of between about 4 mtorr to 8 mtorr.

It is an object of the invention to provide selective etching technologies of SiO₂, titanium and In₂O₃ thin films for MFM_(ox) such as Metal/FE/In₂O₃/Si FeRAM devices.

This summary and objectives of the invention are provided to enable quick comprehension of the nature of the invention. A more thorough understanding of the invention may be obtained by reference to the following detailed description of the preferred embodiment of the invention in connection with the drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a block diagram of the method of the invention.

FIGS. 2-7 depicts steps in the method of the invention.

FIG. 8 is a microphotograph of a device constructed according to the method of the invention, wherein etching of SiO₂ is stopped at a titanium layer.

FIG. 9 is a microphotograph of a device constructed according to the method of the invention, wherein etching of titanium is stopped at a In₂O₃ layer.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The method of the invention includes a selective etching processes of SiO₂ which is stopped by a titanium layer, which titanium layer is then etched, wherein the etching of the titanium layer is stopped by a In₂O₃ thin film. This etching process is particularly suitable for MFM_(ox) (Metal-Ferroelectric-Metal oxide) FeRAM fabrication, although it may be used in other types of device fabrication.

The integration process of the method of the invention 10 is depicted in FIG. 1 and FIGS. 2-8. Referring to FIGS. 1 and 2, a substrate 12 is prepared and an oxide layer 14 is deposited thereon to a thickness of between about 10 nm to 50 nm. Substrate preparation may also include well formation and ion implantation for threshold voltage adjustment.

FIG. 3 depicts the structure following deposition of additional oxide 16 to a thickness of between about 100 nm to 300 nm, after removal of oxide layer 14, followed by patterning and etching of the oxide layer 16, and ion implantation 18 to form source 20 and drain 22.

FIG. 4 depicts the structure following a wet etch of oxide layer 16, deposit of another thin oxide layer 17 to a thickness of between about 10 nm to 50 nm, after removal of oxide layer 16, patterning and wet etch 24 of oxide layer 17, which stops at the level of silicon in substrate 12, followed by deposition of an In₂O₃ layer 26 to a thickness of between about 10 nm to 100 nm and deposition of a titanium layer 28 to a thickness of between about 10 nm to 50 nm.

FIG. 5 shows the structure following patterning and etching of In₂O₃ layer 26 and titanium layer 28, deposition of additional oxide to layer 17, and patterning and etching of oxide layer 17, stopping at the level of titanium layer 28, step 30, which is, in reality, a two step process, described in greater detail later herein.

Referring to FIG. 6, the structure is patterned and wet etched 32 to remove titanium in the gate active region, which etching stops at the level of In₂O₃ layer 26. A layer of SiN 34 is deposited to a thickness of between about 20 nm to 50 nm and etched, leaving a SiN sidewall in the trench overlying the remaining In₂O₃ A layer of ferroelectric material 38, Pb₅Ge₃O₁₁ (PGO) in the preferred embodiment is deposited to a thickness of between about 200 nm to 500 nm on In₂O₃ layer 26. Other ferroelectric materials, such as Pb(Zr, Ti)O₃ (PZT), SrBi₂Ta₂O₃ (SBT) or Bi₄Ti₃O₁₂, may be used. The ferroelectric material is smoothed by chemical mechanical polishing (CMP) 40. A top electrode 42 is deposited on ferroelectric material 38.

FIG. 7 depicts a nearly complete FeRAM device, which includes deposition of additional oxide 44, contact hole formation and metallization 46, resulting in metal contact 48, 50 and 52. Any further processes required to complete the FeRAM structure are then accomplished 54.

The selective etching processes of the method of the invention for SiO₂ titanium and In₂O₃ thin films provide for fabrication of a Metal/FE/In₂O₃/Si ferroelectric memory device. SiO₂ is patterned and etched, stopping at the upper surface of an In₂O₃ layer.

The following etching processes are used for patterning and etching SiO₂, and stopping at an In₂O₃ layer. Table 1 shows the chemistry and etching conditions of recipe A. The etching rates for In, In₂O₃ and SiO₂ thin films are 100 nm, 80 nm and 60 nm/minute respectively. Using recipe A to etch SiO₂ with the intent of stopping at the In₂O₃ thin films resulted in an over-etch of about 10 nm of In₂O₃.

TABLE 1 Recipe A BCL Pressure Items (sccm) Cl (sccm) T_(cp) RF (W) Bias RF (W) (mtorr) Range 10-50 40-80 200-500 100-200 4-8 Preferred 30 60 350 150 6

TABLE 2 Etching Rates for In, In₂O₃ and SiO₂ Thin Films Items In In₂O₃ SiO₂ Ti Etching Rates ~100 ~80 ~60 ~420 (nm/minute)

In order to improve the selective etching processes, two-step etching process is used, beginning with fabrication of a three layer structure of SiO₂/Ti/In₂O₃. In the first step, etching Recipe B, as shown in Table 3, is used to etch SiO₂ and titanium materials. The results show that the etch rate for SiO₂ is about 11 nm/seconds and that the etching rate for titanium is very low, as shown in Table 4. This indicates that Recipe B may be used to etch SiO₂ and stop at the titanium layer with minimal over-etch. The SEM in FIG. 8 depicts a photograph of etching of the SiO₂ layer, which etching stopped at the titanium layer.

TABLE 3 Recipe B C₃F₈ Ar RF Source Pressure Items (sccm) (sccm) (W) RF Bias (W) (mtorr) Range 10-30 20-40 1000-3000 400-800 2-6 Parameters 18 30 1800 600 4

TABLE 4 Etching Rates for SiO₂ and Titanium Thin Films using Recipe B Items SiO₂ Ti Etching Rates ~11 Very Low (nm/second)

In the second step, recipe A is used to etch titanium and In₂O₃. The etching rate for titanium and In₂O₃ materials are 420 nm/minute and 60 nm/minute, respectively, as shown in Table 2. Because there is a clear endpoint for titanium etching, stopping at the level of the In₂O₃ layer, recipe B may be used to etch titanium, stopping at the In₂O₃ layer, with only a few nanometers of over-etch. FIG. 9 is a SEM photograph of titanium etching which stopped at the level of the In₂O₃ layer. A wet etch processes may be used to etch titanium and stopping at the level of a In₂O₃ layer. A wet etching solution, which may be used instead of Recipe A, is H₂O₂+5% NH₄OH, which can etch titanium and which does not appreciably etch In₂O₃.

Thus, a selective etching process for use in fabrication of a FeRAM device has been disclosed. It will be appreciated that further variations and modifications thereof may be made within the scope of the invention as defined in the appended claims. 

1. A method of selectively etching a three-layer structure consisting of SiO₂, In₂O₃, and titanium, comprising: etching the SiO₂, stopping at the titanium layer, using C₃F₈ in a range of between about 10 sccm to 30 sccm; argon in a range of between about 20 sccm to 40 sccm, using an RF source in a range of between about 1000 watts to 3000 watts and an RF bias in a range of between about 400 watts to 800 watts at a pressure in a range of between about 2 mtorr to 6 mtorr; and etching the titanium, stopping at the In₂O₃ layer, using BCl in a range of between about 10 sccm to 50 sccm; chlorine in a range of between about 40 sccm to 80 sccm, a T_(cp) in a range of between about 200 watts to 500 watts at an RF bias in a range of between about 100 watts to 200 watts at a pressure in a range of between about 4 mtorr to 8 mtorr.
 2. A method of fabricating a FeRAM using selective etching comprising: preparing a substrate; depositing an oxide layer on the substrate; patterning and etching the oxide layer provide a trench in a gate active region; depositing a layer of In₂O₃ depositing a layer of titanium on the In₂O₃ patterning and selectively etching the titanium, the In₂O₃ and the oxide, using a two step etching process consisting of: etching the SiO₂, stopping at the titanium layer, using C₃F₈ in a range of between about 10 sccm to 30 sccm; argon in a range of between about 20 sccm to 40 sccm, using an RF source in a range of between about 1000 watts to 3000 watts and an RF bias in a range of between about 400 watts to 800 watts at a pressure in a range of between about 2 mtorr to 6 mtorr; and etching the titanium, stopping at the In₂O₃ layer, using BCl in a range of between about 10 sccm to 50 sccm; chlorine in a range of between about 40 sccm to 80 sccm, a T_(cp) in a range of between about 200 watts to 500 watts at an RF bias in a range of between about 100 watts to 200 watts at a pressure in a range of between about 4 mtorr to 8 mtorr; depositing a layer of SiN; etching the SiN layer to leave a sidewall only in the trench; depositing a ferroelectric material in the trench; depositing a top electrode and top oxide material; and completing the FeRAM device.
 3. The method of claim 2 wherein said depositing a ferroelectric material includes depositing a layer ferroelectric material taken from the group of ferroelectric materials consisting of Pb₅Ge₃O₁₁ (PGO), Pb(Zr, Ti)O₃ (PZT), SrBi₂Ta₂O₃ (SBT) and Bi₄Ti₃O₁₂.
 4. A method of fabricating a FeRAM using selective etching comprising: preparing a substrate; depositing an oxide layer on the substrate; patterning and etching the oxide layer provide a trench in a gate active region; depositing a layer of In₂O₃ depositing a layer of titanium on the In₂O₃ patterning and selectively etching the titanium, the In₂O₃ and the oxide, using a two step etching process consisting of: etching the SiO₂, stopping at the titanium layer, using C₃F₈ at 18 sccm; argon at 30 sccm, using an RF source at 1800 watts and an RF bias of 600 watts at a pressure of 3 mtorr; and etching the titanium, stopping at the In₂O₃ layer, using BCl at 30 sccm; chlorine at 60 sccm, a T_(cp) of 350 watts at an RF bias of 150 watts at a pressure of 6 mtorr; depositing a layer of SiN; etching the SiN layer to leave a sidewall only in the trench; depositing a ferroelectric material in the trench; depositing a top electrode and top oxide material; and completing the FeRAM device.
 5. The method of claim 4 wherein said depositing a ferroelectric material includes depositing a layer ferroelectric material taken from the group of ferroelectric materials consisting of Pb₅Ge₃O₁₁(PGO), Pb(Zr, Ti)O₃(PZT), SrBi₂Ta₂O₃(SBT) and Bi₄Ti₃O₁₂. 